The　precipitation　processes　of　CuO-CeO2　catalysts　preparation　were　modified,　and　their　optimized　copper　content　were　also　studied　in　detail.　As　indicated　by　the　experimental　results,　the　WGS　catalytic　activities　of　the　CuO-CeO2　catalysts　can　be　ranked　as:　stepwise　precipitation　(SP)　＞　deposition-precipitation　(DP)　＞　co-precipitation　(CP),　suggesting　that　stepwise　precipitation　(i.e.,　a　modified　DP)　is　a　convenient　and　effective　method　to　prepare　CuO-CeO2　WGS　catalysts.　The　optimized　copper　contents　of　CuO-CeO2-SP　and　CuO-CeO2-CP　catalysts　are　20　wt.%　and　25　wt.%,　respectively.　Their　catalytic　activities　can　be　strongly　correlated　with　the　results　from　XRD,　XPS,　Raman,　N-2-physisorption,　N2O　chemisorption　and　H-2-TPR.　For　DP　and　SP,　a　certain　amount　of　copper　has　substitutively　incorporated　into　ceria　lattice　with　multiple　Ce3+　and　oxygen　vacancies,　which　is　considered　as　one　relatively　strong　interaction　between　copper　and　ceria　support.　The　substitutional　incorporation　of　copper　creates　larger　lattice　distortion,　lattice　defect　(embodying　as　larger　lattice　cell　contraction　of　CeO2,　microstrain　and　Raman　shift)　and　stronger　reducibility　(i.e.,　lower　reduction　temperature　of　H2-TPR),　as　a　consequence,　higher　surface　energy　and　catalytic　activity　for　WGS　reaction.　While　for　CP,　copper　nitrate　and　cerium　nitrate　were　simultaneously　precipitated,　resulting　in　the　burial　of　many　copper　species　in　ceria　supports,　i.e.,　occupancy　incorporation　of　isolated　copper　into　ceria　lattice　vacant　site,　which　is　considered　as　another　weak　interaction　between　copper　and　ceria　support.　Accordingly,　combined　with　N2O　chemisorption　results,　it　is　demonstrated　that　surface　copper　species　of　CuO-CeO2-CP　are　fewer　and　less　active　than　those　of　CuO-CeO2-DP　and　CuO-CeO2-SP.　Lastly,　there　is　a　direct　relationship　between　the　pore　volume　along　with　most　probable　pore　size　of　the　as-synthesized　catalysts　and　their　corresponding　catalytic　activities　for　WGS　reaction.　Copyright　(C)　2014,　Hydrogen　Energy　Publications,　LLC.　Published　by　Elsevier　Ltd.　All　rights　reserved.